Blends of polyphenylene sulfones and polyphenylene sulfide resins

Abstract

blends of a polyphenylene sulfone (PPSU); a polyphenylene sulfide (PPS); and, a polyetherimide and epoxy. The polyetherimide and epoxy are present in an amount effective to act as a compatibilizer for the polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS). Methods of compatibilizing a blend of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS). The method can include melt mixing a polyphenylene sulfone (PPSU) and a polyetherimide; and melt mixing a polyphenylene sulfide (PPS) and an epoxy.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Non-Provisional of U.S. Application Ser. No. 61/749,177, having been filed on Jan. 4, 2013, herein incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

There has long been interest in developing thermoplastic blends containing semi-crystalline and amorphous materials that exhibit chemical resistance and good mechanical property retention at high temperature. Many semi-crystalline polymer blends demonstrate excellent chemical resistance and are well known in the art. However, the addition of neat amorphous materials to obtain high temperature property retention is not as well known or documented in the literature. These polymer blends generally tend to be incompatible and difficult to compound without the addition of fillers or additives such as glass, talc or mica. When a compatible unfilled resin blend is desired, it is often necessary to add a small amount of another ingredient or compatibilizer to promote more thorough blending between the two polymers. The additional ingredient(s) may work by promoting bond formation between the diverse polymer molecules of each material. It is very difficult to determine what ingredient(s) may work since compatibilizers that are effective in one polymer blend system may not be effective in others; a great deal depends upon the chemistry and specific functionalities of the molecules being blended and their interaction.

The reason for blending polymers is to create compositions that are better at meeting a specific need than an individual polymer or a polymer blend known in the art. Accordingly, it is sometimes desired to combine a polymer with another in the hopes of creating a blend exhibiting the desired characteristics of both polymers. In the present invention, polyphenylene sulfide (PPS) demonstrates excellent chemical resistance and good thermal stability which may potentially be important for polymer blends desiring such characteristics. In addition, polyphenylene sulfones (PPSU) exhibit excellent mechanical property retention at high temperature. The combination of these material properties is highly desirable, however PPSU and PPS are incompatible and therefore material blends are very difficult to compound and make into commercial products. The PPSU/PPS blends tend to have a morphology with large regions or domains of the individual polymers rather than fine, well-dispersed domains. The large domains tend to produce a material with poor mechanical properties, e.g. injection molded parts having poor tensile properties.

BRIEF SUMMARY OF THE INVENTION

Various embodiments relate to the preparation of forming compatible immiscible phase-separated blends of polyphenylene sulfones (PPSU) and polyphenylene sulfides (PPS). The new resin blend adds polyetherimide (PEI) with an epoxy to compatibilize the blend and significantly improve material properties. The new resin blend demonstrates excellent mechanical and thermal properties as well as having good melt flow characteristics. The phase-separated blends improves the high temperature load bearing capability and dimensional stability of PPS and melt flow, chemical resistance and flame resistance properties of PPSU.

Various embodiments describe a process by which a PPS resin having reactive end groups (such as thiol and chlorine) is compatibilized with PPSU resin, or derivatives thereof, using a mixture of PEI and epoxies as compatibilizers. In this invention two polymers are blended and melt mixed with compatibilizers and extruded into a pellet.

Various embodiments provide a process for forming compatible PPS blends with other thermoplastic materials that are either amorphous or semi-crystalline in nature. Other embodiments provide a process for reactive compatibilizing of PPSU and PPS materials. It is also understood, the blends material properties such as melt flow, impact and thermal resistance, chemical resistance, electrical properties and flame resistance can be tailored as desired by varying the compositions of the individual constituents, PPS, PPSU, PEI and epoxy.

These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention as well as to the examples included therein. All numeric values are herein assumed to be modified by the term “about,” whether or not explicitly indicated. The term “about” generally refers to a range of numbers that one of skill in the art would consider equivalent to the recited value (i.e., having the same function or result). In many instances, the term “about” may include numbers that are rounded to the nearest significant figure.

Various embodiments relate to a composition comprising a blend of: a polyphenylene sulfone (PPSU); a polyphenylene sulfide (PPS); and, a polyetherimide and epoxy, wherein the polyetherimide and epoxy are present in an amount effective to act as a compatibilizer for the polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS).

The composition can have within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, and 400 MPa. For example, according to certain preferred embodiments, the composition can have a tensile strength greater than 75 MPa.

The composition can have within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, and 400 J/m. For example, according to certain preferred embodiments, the composition can have an impact strength of at least 40 J/m.

The composition can have within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100%. For example, according to certain preferred embodiments, the composition can have an elongation at break of at least 70%.

The epoxy can be an multi-functional epoxies for example, according to certain preferred embodiments, the composition can have an epoxy cresol Novolac resin.

The polyphenylene sulfide (PPS) can be a linear poly(phenylene) sulfide.

The morphology of the composition can be fine, well-dispersed domains of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS).

The polyetherimide can be present in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, and 30 weight percent based on the total weight of the composition. For example, according to certain preferred embodiments, the polyetherimide can be present in an amount of from 2.5-15 weight percent based on the total weight of the composition.

The epoxy can be present in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 weight percent based on the total weight of the composition. For example, according to certain preferred embodiments, the epoxy can be present in an amount of from 0.5-1.5 weight percent based on the total weight of the composition.

The composition can exhibit a heat distortion temperature (HDT) within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 260, 270, 280, 290, and 300 degrees Celsius. For example, according to certain preferred embodiments, the composition can exhibit a heat distortion temperature (HDT) of at least 87 degrees Celsius

The polyphenylene sulfone (PPSU) can be present in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 62, 62.5, 63, 63.5, 64, 64.5, 65, 65.5, 66, 66.5, 67, 67.5, 68, 68.5, 69, 69.5, 70, 70.5, 71, 71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81, 81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, and 90 weight percent based on the total weight of the composition. For example, according to certain preferred embodiments, the polyphenylene sulfone (PPSU) can be present in an amount of from 24.5-74.5 weight percent based on the total weight of the composition.

The polyphenylene sulfide (PPS) can be present in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 62, 62.5, 63, 63.5, 64, 64.5, 65, 65.5, 66, 66.5, 67, 67.5, 68, 68.5, 69, 69.5, 70, 70.5, 71, 71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81, 81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, and 90 weight percent based on the total weight of the composition. For example, according to certain preferred embodiments, the polyphenylene sulfide (PPS) can be present in an amount of from 25-74.5 weight percent based on the total weight of the composition.

Various embodiments relate to an extrudate comprising the composition according to other embodiments described herein. Various embodiments relate to a molded product comprising the composition according to other embodiments described herein.

Another embodiment relates to a method of compatibilizing a blend of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS). The method can include a) melt mixing a polyphenylene sulfone (PPSU) and a polyetherimide; and b) melt mixing a polyphenylene sulfide (PPS) and an epoxy. The melt mixing a polyphenylene sulfone (PPSU) and a polyetherimide; and the melt mixing a polyphenylene sulfide (PPS) and an epoxy can be carried out by one of the group consisting of sequential mixing and simultaneous mixing.

The method can be performed by a two pass method, in which an initial mixture of step a) is formed in an initial pass in an extruder and step b) is performed in a second pass through the extruder.

According to various embodiments, steps a) and b) can be performed in a single pass in an extruder or performed in a twin screw, vented extruder. The screws of the twin screw, vented extruded can be run at a rotation within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 405, 410, 415, 420, 425, 430, 435, 440, 445, 450, 455, 460, 465, 470, 475, 480, 485, 490, 495, and 500 rotations per minute (rpm) under vacuum. For example, according to certain preferred embodiments, the screws of the twin screw, vented extruded can be run at a rotation of about 250 rotations per minute (rpm) under vacuum.

According to various embodiments, steps a) and b) can be performed at a temperature within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 degrees Celsius. For example, according to certain preferred embodiments, according to various embodiments, steps a) and b) can be performed at a temperature in the range of 300 to 360 degrees Celsius.

According to various embodiments step a) can be performed at a temperature within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 340.5, 341, 341.5, 342, 342.5, 343, 343.5, 344, 344.5, 345, 345.5, 346, 346.5, 347, 347.5, 348, 348.5, 349, 349.5, 350, 350.5, 351, 351.5, 352, 352.5, 353, 353.5, 354, 354.5, 355, 355.5, 356, 356.5, 357, 357.5, 358, 358.5, 359, 359.5, 360, 360.5, 361, 361.5, 362, 362.5, 363, 363.5, 364, 364.5, 365, 365.5, 366, 366.5, 367, 367.5, 368, 368.5, 369, 369.5, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 degrees Celsius. For example, according to certain preferred embodiments, according to various embodiments step a) can be performed at a temperature in the range of 350 to 360 degrees Celsius.

According to various embodiments step b) can be performed at a temperature within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 320.5, 321, 321.5, 322, 322.5, 323, 323.5, 324, 324.5, 325, 325.5, 326, 326.5, 327, 327.5, 328, 328.5, 329, 329.5, 330, 330.5, 331, 331.5, 332, 332.5, 333, 333.5, 334, 334.5, 335, 335.5, 336, 336.5, 337, 337.5, 338, 338.5, 339, 339.5, 340, 340.5, 341, 341.5, 342, 342.5, 343, 343.5, 344, 344.5, 345, 345.5, 346, 346.5, 347, 347.5, 348, 348.5, 349, 349.5, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 degrees Celsius. For example, according to certain preferred embodiments, according to various embodiments step b) can be performed at a temperature of 330 to 340 degrees Celsius.

Various embodiments relate to a method of compatibilizing a blend of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS). The method can include step a) melt mixing a polyphenylene sulfide (PSU), a polyetherimide and an epoxy to form an initial mixture; and step b) melt mixing the initial mixture of step a) with a polyphenylene sulfone (PPSU). According to various embodiments, steps a) and b) can be performed in a vented, twin screw extruder.

According to various embodiments step a) can be performed at a temperature within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 330.5, 331, 331.5, 332, 332.5, 333, 333.5, 334, 334.5, 335, 335.5, 336, 336.5, 337, 337.5, 338, 338.5, 339, 339.5, 340, 340.5, 341, 341.5, 342, 342.5, 343, 343.5, 344, 344.5, 345, 345.5, 346, 346.5, 347, 347.5, 348, 348.5, 349, 349.5, 350, 350.5, 351, 351.5, 352, 352.5, 353, 353.5, 354, 354.5, 355, 355.5, 356, 356.5, 357, 357.5, 358, 358.5, 359, 359.5, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 degrees Celsius. For example, according to certain preferred embodiments, according to various embodiments step a) can be performed at a temperature in the range of 340 to 350 degrees Celsius.

According to various embodiments step b) can be performed at a temperature within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 330.5, 331, 331.5, 332, 332.5, 333, 333.5, 334, 334.5, 335, 335.5, 336, 336.5, 337, 337.5, 338, 338.5, 339, 339.5, 340, 340.5, 341, 341.5, 342, 342.5, 343, 343.5, 344, 344.5, 345, 345.5, 346, 346.5, 347, 347.5, 348, 348.5, 349, 349.5, 350, 350.5, 351, 351.5, 352, 352.5, 353, 353.5, 354, 354.5, 355, 355.5, 356, 356.5, 357, 357.5, 358, 358.5, 359, 359.5, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 degrees Celsius. For example, according to certain preferred embodiments, according to various embodiments step b) can be performed at a temperature in the range of 340 to 350 degrees Celsius.

EXAMPLES

Table 1 summarizes materials employed in the examples.

TABLE 1
Material	Description	Source
Polyphenylene Sulfone	Radel R ® 5100NT	Solvay
(PPSU)
Polyetherimide (PEI)	ULTEM ® 1010	SABIC
		Innovative
		Plastics
Linear poly(phenylene sulfide)	Fortron ® 0214B	Ticona
(PPS)
Polymeric compound with 24	Joncryl ® ADR4368	BASF
pendant epoxy per molecule
(avg)
Epoxy cresol novolac resin	Poly(o-cresyl glycidyl	Aldrich
(ECN)	ether)-co-
	formaldehyde

Techniques & Procedures
Composition Preparation Techniques:

Resin blend compositions were formed by melt mixing of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS). The resin blends were compounded by extrusion in a 2.5-inch twin screw, vacuum vented extruder. Material blends evaluated are presented in tabular form with each constituent reported on a weight percent basis of the total. The extruder temperature was profiled and ranged from 300 to 350° C. at the feed throat and die respectively. The blends were extruded at 250 rotations per minute (rpm) under vacuum. Resin blends were made using one of three compounding methods, 1) a single pass method as described above, 2) two pass method in which PPSU and PEI were melt mixed at 350 to 360° C. to form an initial mixture and then subsequently melt mixed with PPS and ECN resins at 330 to 340° C. or 3) modified two pass method in which PEI, PPS and ECN resins were melt mixed at 340 to 350° C. to form an initial mixture and then melt mixed with PPSU at 340 to 350° C. Independent of the compounding method used, the extrudate was water cooled, chopped and pelletized. The resin was dried at 150° C. in preparation for injection molding of test samples. Resin blends were injection molded into ASTM test samples using a barrel temperature setting of 340 to 350° C. with mold temperature settings of 80 to 150° C. and 30 second cycle time.

Properties Testing

Properties were measured using ASTM test methods. All molded samples were conditioned for at least 48 hours at 50% relative humidity prior to testing.

ASTM D256: Notched Izod impact values were measured at room temperature on 3.2 millimeter thick bars as per ASTM D256. Bars were notched prior to oven aging and tested at room temperature. Results are reported in Joules per meter (J/m).

ASTM D638: Tensile properties were measured on 3.2 millimeter type I bars as per ASTM method D638 at 23° C. with a crosshead speed of 5 millimeters/minute. Tensile strength is reported at yield (Y) while percent elongation (% Elongation) is reported at break (B). Tensile modulus, tensile strength at yield and tensile strength at break results are reported in MPa.

ASTM 0648: Heat Deflection Temperature (HDT) was measured on a 3.2 millimeter injection molded bar at 1.82 MPa Stress. HDT is reported in degree Celsius (C).

Results

According to various embodiments PPSU and PPS resin blends and the excellent compatibility of these materials as a result of adding PEI and ECN as compatibilizers. The amount of PEI in the blend was limited to less than 25 wt % while epoxy ranged from 0.5 to 1.5 wt %. The blends exhibits excellent processibility with improved tensile and impact resistance properties. The new compatibilized PPSU/PPS blends demonstrate improved mechanical, thermal and melt flow properties over a range of compositions as presented in the following tables.

Examples 1-12

The purpose of examples 1-12 was to demonstrate the effect of changing the amounts and types of polymeric compatibilizers in compositions having PPSU and PPS resins. Compositions were made in accordance to the composition preparation procedure described above. The compositions were tested as described above and results are shown in Tables 2A and 2B.

TABLE 2A
Polymer Type	1*	2	3*	4*	5*	6
PPSU	25	24.5	24.5	20	50	49.5
PPS	75	74.5	74.5	70	50	49.5
PEI				10
ECN		1		1		1
Joncryl ADR			1
4368
Tensile strength	66	75	74	68	67	75
(MPa)
Tensile modulus	3068	3292	2957	3281	2817	2776
(GPa)
% Elongation	5	77	42	4	84	88
Flexural modulus	2522	2581	2564	2657	2326	2438
(GPa)
Flexural strength	104	110	110	109	105	111
(MPa)
MFR 337° C.,	108	32	41	79	61	14
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	86	87	89	88	95	102
Notched Izod	28	43	40	14	31	69
Impact (J/m)
*Comparative Example

TABLE 2B
Polymer Type	7*	8*	9*	10	11*	12*
PPSU	49.5	45	75	74.5	74.5	70
PPS	49.5	45	25	24.5	24.5	20
PEI		10				10
ECN				1
Joncryl ADR	1				1
4368
Tensile strength	73	70	70	77	74	75
(MPa)
Tensile modulus	2683	2604	2292	2408	2471	2739
(GPa)
% Elongation	87	49	60	70	25	64
Flexural modulus	2461	2549	2385	2445	2461	2521
(GPa)
Flexural strength	109	113	109	113	114	112
(MPa)
MFR 337° C.,	15	63	17	13	9	15
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	100	99	156	157	158	165
Notched Izod	60	32	113	132	147	102
Impact (J/m)
*Comparative Example

These examples demonstrate that only by using a Novolac epoxy (ECN) resin in the required amount yields a composition capable of achieving a combination of a tensile strength greater than or equal to 75 MPa, impact strength of greater than or equal to 40 J/m, heat deflection temperature greater than or equal to 85° C. and an elongation at break greater than or equal to 70%. This is valid over a composition range of 25-75 wt % PPSU and 25-75 wt % PPS.

Examples 12-23

The purpose of examples 12-23 was to demonstrate the effect of changing the amounts of Novolac epoxy resin as well as the effect of alternate polymeric compounds having pendant epoxy groups in compositions having PPS and PPSU resins. Compositions were made in accordance with the composition preparation procedure described above. The compositions were tested as described above and results are shown in Tables 3A and 3B.

TABLE 3A
Polymer	12*	13*	14	15*	16*	17*
PPSU	25	24.75	24.5	24.25	50	49.75
PPS	75	74.75	74.5	74.25	50	49.75
ECN		0.5	1	1.5		0.5
Tensile strength	66	75	75	73	67	74
(MPa)
Tensile modulus	3068	3013	3292	2941	2817	3275
(GPa)
% Elongation	5	3	77	79	84	70
Flexural strength	104	122	110	119	105	126
(MPa)
Flexural modulus	2522	2682	2581	2848	2326	3082
(GPa)
MFR 337° C.,	108	61	32	16	61	13
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	86	87	87	84	102	105
Notched Izod	28	40	46	43	31	47
Impact (J/m)
*Comparative Example

TABLE 3B
Polymer	18	19*	20*	21*	22	23*
PPSU	49.5	49.25	75	74.75	74.5	74.25
PPS	49.5	49.25	25	24.75	24.5	24.25
ECN	1	1.5		0.5	1	1.5
Tensile strength	75	72	70	73	77	73
(MPa)
Tensile modulus	2776	2489	2292	2837	2406	2469
(GPa)
% Elongation	88	68	60	60	70	55
Flexural strength	111	116	109	119	113	116
(MPa)
Flexural modulus	2438	2551	2385	2852	2445	2581
(GPa)
MFR 337° C.,	14	14	17	23	13	13
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	102	103	156	158	157	155
Notched Izod	69	59	113	62	132	138
Impact (J/m)
*Comparative Example

These examples demonstrate only using a Novolac epoxy (ECN) resin in the required amount yields a composition capable of achieving a combination of a tensile strength greater than or equal to 75 MPa, impact strength of greater than or equal to 40 J/m, Heat deflection temperature greater than or equal to 85° C. and an elongation at break greater than or equal to 70%. This shows there is an optimum level of ECN epoxy resin for composition ranges of 25-75 wt % PPSU and 25-75 wt % PPS.

Examples 24-35

The purpose of Examples 24-35 was to demonstrate the effect of changing amounts of PEI having PPS as the constituent in the majority. Compositions were made in accordance with the two pass method described above. For compositions not containing the Novolac epoxy (ECN) resin, only the PPS was added to the initial mixture. The compositions were tested as described above and results are shown in Tables 4A and 4B.

These results show with increasing amounts of PEI from 2.5 to 15 wt % and with

TABLE 4A
Polymer	24*	25	26*	27	28*	29
PPSU	22.5	22.25	20	19.5	18.5	18.25
PEI	2.5	2.5	5	5	7.5	7.5
PPS	75	74.25	75	74.5	74	73.25
ECN		1		1		1
Tensile strength	68	73	73	74	69	76
(MPa)
Tensile modulus	2988	3218	3162	3243	3166	3184
(GPa)
% Elongation	4	48	4	85	4	79
Flexural strength	113	116	114	114	106	111
(MPa)
Flexural modulus	2959	2877	2990	2801	2890	2806
(GPa)
MFR 337° C.,	120	21	119	19	126	21
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	97	95	92	91	84	88
Notched Izod	27	43	28	42	28	54
impact (J/m)
*Comparative Example

TABLE 4B
Polymer	30*	31	32*	33	34*	35
PPSU	45	44.5	40	39.5	35	34.5
PEI	5	5	10	10	15	15
PPS	50	49.5	50	49.5	50	49.5
ECN		1		1		1
Tensile strength	58	76	65	76	76	77
(MPa)
Tensile modulus	2661	3091	2861	3109	2991	3095
(GPa)
% Elongation	56	80	27	88	13	77
Flexural strength	116	124	117	116	115	121
(MPa)
Flexural modulus	2804	2899	2794	2720	2724	2790
(GPa)
MFR 337° C.,	66	9	73	9	71	7
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	119	120	115	118	118	119
Notched Izod	36	50	37	66	38	68
Impact (J/m)
*Comparative Example

1 wt % Novolac epoxy (ECN) resin, the compositions still achieves the desired levels of tensile strength, impact strength, HDT and % elongation performance.

A comparison of Examples 24-35 shows compositions comprising of PPSU, PPS and PEI there is a marked increase in tensile strength, elongation at break and impact strength in the presence of a ECN epoxy resin. Comparative examples show this improvement is not seen in examples comprising a PPSU, PPS and PEI without the epoxy and also none of the compositions have a combination of a tensile strength greater than or equal to 70 MPa, impact strength of greater than or equal to 40 J/m, and an elongation at break greater than or equal to 45%.

The results are further unexpected because (as evidenced by the % Elongation at break and impact strength results) the combination of a PPS, PEI and PPSU (they are immiscible and incompatible) when used in conjunction with ECN epoxy resin having an average of 2 or more epoxy groups per molecule, produce a composition that exhibits a ductility higher than the ductility of the PPS individually in PPS rich compositions.

Examples 36-41

The purpose of Examples 36-41 was to demonstrate the effect of changing amounts PEI in PPSU rich compositions. Compositions were made in accordance with the two pass method described above. For compositions not containing the Novolac epoxy resin (ECN), only the PPS was added to the initial mixture. The compositions were tested as described above and results are shown in Table 5.

TABLE 5
Polymer	36*	37	38*	39	40*	41
PPSU	67.5	67	60	59.5	52.5	52
PEI	7.5	7.5	15	15	22.5	22.5
PPS	25	24.5	25	24.5	25	24.5
ECN		1		1		1
Tensile strength	75	78	76	78	79	84
(MPa)
Tensile modulus	2627	2856	2764	2940	2811	2932
(GPa)
% Elongation	75	80	80	89	68	90
Flexural strength	2590	2677	2802	2740	2635	2693
(MPa)
Flexural modulus	115	122	121	126	121	129
(GPa)
MFR 337° C.,	17	14	18	12	21	11
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	162	160	165	165	169	170
Notched Izod	134	154	80	115	82	96
Impact (J/m)
*Comparative Example

These results show that with increasing amounts of PEI the compositions still achieve the desired levels of tensile strength, impact strength, and elongation.

Examples 42-53

The purpose of Examples 42-53 was to demonstrate the effect of differing amounts of Novolac epoxy (ECN) resin as well as the effect of alternate polymeric compounds having pendant epoxy groups in compositions having PPS, PEI and PPSU resins. Compositions were made by two step method with the composition preparation procedure described above. The compositions were tested as described above and results are shown in Table 6.

TABLE 6A
Polymer	42*	43*	44	45*	46*	47*
PPSU	52.5	52.25	52	52.25	35	34.75
PEI	22.5	22.5	22.5	22.5	15	15
PPS	25	24.75	24.5	23.75	50	49.75
ECN		0.5	1	1.5		0.5
Tensile strength	79	77	84	79	76	73
(MPa)
Tensile modulus	2811	2724	2932	2734	2991	2904
(GPa)
% Elongation	68	81	90	64	13	96
Flexural strength	2635	116	2693	119	115	113
(MPa)
Flexural modulus	121	2543	129	2537	2724	2667
(GPa)
MFR 337° C.,	21	16	11	14	71	12
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	169	169	170	170	118	117
Notched Izod	82	90	96	99	38	54
Impact (J/m)
*Comparative Example

TABLE 6B
Polymer	48	49*	50*	51*	52	53*
PPSU	34.5	34.25	18.5	18.25	18	17.75
PEI	15	15	7.5	7.5	7.5	7.5
PPS	49.5	49.25	74	73.75	73.5	73.25
ECN	1	1.5		0.5	1	1.5
Tensile	77	74	69	71	76	74
strength
(MPa)
Tensile	3095	2946	3166	3039	3184	3090
modulus
(GPa)
% Elongation	77	84	4	4	79	31
Flexural	121	117	106	106	111	108
strength
(MPa)
Flexural	2790	2658	2890	2690	2806	2741
modulus
(GPa)
MFR 337° C.,	7	9	126	36	21	25
6.7 Kg, 5 min
(g/10 min)
HDT	119	118	86	86	88	84
(1.82 MPa)
Notched Izod	68	63	28	50	54	55
Impact (J/m)
*Comparative Example

These results show that with increasing amounts of PEI the compositions still achieve the desired levels of tensile strength, impact strength, and elongation.

Examples 54-59

The purpose of examples 54-59 was to demonstrate the effect of the process used to make the composition on the final physical properties of the composition. Compositions were made in a one pass method (in accordance to the composition preparation procedure described above) or a two pass method in which PPSU and PEI were melt mixed at 350 to 360° C. to form an initial mixture and then the initial mixture was melt mixed with the PPS and Novolac epoxy (ECN) resin at 330 to 340° C. or a modified two pass method in which PEI, PPS and Novolac epoxy resin were melt mixed at 340 to 350° C. to form an initial mixture and then melt mixed with PPSU resin at 340 to 350° C. The compositions were tested as described above and results are shown in Table 7.

TABLE 7
					Modified	Modified
	One pass	One pass	Two pass	Two pass	Two Pass	Two Pass
Polymer	54*	55*	56*	57	58*	59*
PPSU	52.5	52	52.5	52	52.5	52
PEI	25	22.5	22.5	22.5	22.5	22.5
PPS	22.5	24.5	25	24.5	25	24.5
ECN		1		1		1
Tensile strength	75	75	79	84	45	76
(MPa)
Tensile modulus	2752	2799	2811	2932	3302	3360
(GPa)
% Elongation	45	60	68	90	9	19
Flexural strength	2582	2665	2635	2693	117	113
(MPa)
Flexural modulus	118	120	121	129	3053	3231
(GPa)
MFR 337° C.,	20	17	21	11	66	69
6.7 Kg, 5 min
(g/10 min)
HDT (1.82 MPa)	164	165	169	170	86	87
Notched Izod	75	82	82	96	33	33
Impact (J/m)
*Comparative Example

Compositions made with the two pass method showed a greater increase in tensile strength, elongation at break, and impact strength than compositions made with the one pass method and modified two pass method.

Addition of epoxy shows good improvement in the tensile and impact strength compare to the control blends in some PPS rich and PPSU rich compositions. Two different types of multifunctional epoxies have been evaluated as a compatibilizer in PPSU/PPS system. The amount of epoxy in the composition varied from 0.5 to 1.5 wt % and 1% was found to optimum level to show enhancement in the properties like tensile and impact properties. Also the blends shows better flow performance compare to PPSU resin.

It has been found that, by addition of PEI as third component with or without epoxy to PPSU/PPS blends leads to an improvement in impact and tensile strength properties of the blend in comparison with neat PPSU and PPS blends. It is likely that PEI acts as a compatibilizing agent for PPSUIPPS blends especially in PPSU rich blends. It is expected that other polyetherimides such as Extem XH 1005, VH 1003, Ultem 6000, Siltem and Ultem 5001 resins would also be a good compatibilizer for the PPSU/PPS blends.

To make a secondary (PPSU/PPS) or ternary blend (PPSU/PEI/PPS) blends, one can blend all three components and extrude in one-pass. Alternatively, in a two-pass process, two of the components (e.g., PPSU and PEI) could be extruded first and then PPS and ECN added in the second pass. The two pass helps to get better compatibility than one pass and modified two pass, due to better reactivity of end groups with the compatibilizer.

Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein.

The reader's attention is directed to all papers and documents which are filed concurrently with this specification and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

All the features disclosed in this specification (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

Any element in a claim that does not explicitly state “means for” performing a specified function, or “step for” performing a specific function, is not to be interpreted as a “means” or “step” clause as specified in 35 U.S.C §112, sixth paragraph. In particular, the use of “step of” in the claims herein is not intended to invoke the provisions of 35 U.S.C §112, sixth paragraph.

Claims

1. A compatibilized blend of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS) comprising:

a) 20-77 wt % of a polyphenylene sulfone (PPSU);

b) 20-77 wt % of a polyphenylene sulfide (PPS);

c) 2.5-22.5 wt % a polyetherimide compatibilizer; and

d) 0.5-1.5 wt % an epoxy compatibilizer;

wherein the amounts of a), b), c), and d) are based on the overall weight of the compatibilized blend and together account for 100 wt % of the compatibilized blend.

2. The compatibilized blend of claim 1, wherein the compatibilized blend possesses a tensile strength greater than 75 MPa, an impact strength of at least 40 J/m, and an elongation at break of at least 70%.

3. The compatibilized blend of claim 1, wherein the epoxy compatibilizer is an epoxy cresol novolac resin.

4. The compatibilized blend of claim 1, wherein the polyphenylene sulfide (PPS) is a linear poly(phenylene) sulfide.

5. The compatibilized blend of claim 1, wherein the morphology of the compatibilized blend comprises fine, well-dispersed domains of polyphenylene sulfone (PPSU) and polyphenylene sulfide (PPS).

6. The compatibilized blend of claim 1, wherein the compatibilized blend exhibits a heat distortion temperature (HDT) of at least 87° C.

7. The compatibilized blend of claim 1 comprising:

a) 24.5-74.5 wt % of the polyphenylene sulfone (PPSU);

b) 24.5-74.5 wt % of the polyphenylene sulfide (PPS);

c) 2.5-22.5 wt % of the polyetherimide compatibilizer; and

d) 0.5-1.5 wt % of the epoxy compatibilizer;

wherein the amounts of a), b), c), and d) are based on the overall weight of the compatibilized blend and together account for 100 wt % of the compatibilized bend.

8. An extrudate of the compatibilized blend of claim 1.

9. A molded product of the compatibilized blend of claim 1.

10. A method of preparing the compatibilized blend of claim 1, comprising:

melt mixing the polyphenylene sulfone (PPSU), the polyphenylene sulfide (PPS), the polyetherimide compatibilizer, and the epoxy compatibilizer in a single pass through an extruder.

11. The method of claim 10, wherein the extruder is a twin screw, vented extruder.

12. The method of claim 11, wherein melt mixing is performed at a temperature of 300 to 350° C.

13. The method of claim 11, wherein melt mixing is performed at a screw speed of about 250 rotations per minute (rpm) and vented under vacuum.

14. A method of preparing the compatibilized blend of claim 1, comprising:

(a) melt mixing the polyphenylene sulfone (PPSU) and the polyetherimide compatibilizer in a first pass through an extruder to form an initial mixture; and

(b) melt mixing the initial mixture with the polyphenylene sulfide (PPS) and the epoxy compatibilizer in a second pass through the extruder.

15. The method of claim 14, wherein the extruder is a twin screw, vented extruder.

16. The method of claim 15, wherein melt mixing of step a) is performed at a temperature of 350 to 360° C., and melt mixing of step b) is performed at a temperature of 330 to 340° C.

17. The method of claim 15, wherein melt mixing of step a) and melt mixing of step b) are performed at a screw speed of about 250 rotations per minute (rpm) and vented under vacuum.

18. A method of preparing the compatibilized blend of claim 1, comprising:

a) melt mixing the polyphenylene sulfide (PPS), the polyetherimide compatibilizer, and the epoxy compatibilizer in a first pass through an extruder to form an initial mixture; and

b) melt mixing the initial mixture with the polyphenylene sulfone (PPSU) in a second pass through the extruder.

19. The method of claim 18, wherein the extruder is a vented, twin screw extruder.

20. The method of claim 19, wherein melt mixing of step a) and melt mixing of step b) are performed at a temperature of 340 to 350° C.

21. The method of claim 19, wherein melt mixing of step a) and melt mixing of step b) are performed at a screw speed of about 250 rotations per minute (rpm) and vented under vacuum.